Production of hollow ceramic membranes by electrophoretic deposition

• US 6,607,645 B1
• Filed: 05/31/2000
• Issued: 08/19/2003
• Est. Priority Date: 05/10/2000
• Status: Expired due to Term

• Current Assignee: Innotech Alberta Inc.
• Original Assignee: Alberta Research Council Inc. (Alberta Science & Research Authority)
• Inventors: Sarkar, Partha
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): TRAN, THAO T
• Application Number:
  US09/583,274
• Time in Patent Office: 1,175 Days
• Field of Search: 204/483, 204/484, 204/507, 204/509
• US Class Current: 204/483
• CPC Class Codes: C04B 14/303 Alumina
• CPC Class Codes: C04B 2111/00413 Materials having an inhomogeneous concentration of ingredients or irregular properties in different layers
• CPC Class Codes: C04B 2111/00801 Membranes; Diaphragms
• CPC Class Codes: C04B 2111/00853 in electrochemical cells or batteries, e.g. fuel cells
• CPC Class Codes: C04B 30/02 containing fibrous materials
• CPC Class Codes: C04B 35/00 Shaped ceramic products characterised by their composition porous ceramic products C04B38/00; ceramic articles characterised by particular shape, see the relevant classes, e.g. linings for casting ladles, tundishes, cups or the like B22D41/02; ceramic substrates for microelectronic semi-conductors H01L23/15; Ceramics compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides other than as macroscopic reinforcing agents C22C; shaping of ceramics B28B; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products chemical preparation of powders of inorganic compounds C01; infiltration of sintered ceramic preforms with molten metal C04B41/51
• CPC Class Codes: C04B 38/00 Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof treating slag with gases or gas generating material C04B5/06 ; expanded graphite C04B35/536
• CPC Class Codes: C04B 38/0003 containing continuous channels, e.g. of the "dead-end" type or obtained by pushing bars in the green ceramic product B28B takes precedence
• CPC Class Codes: C04B 38/007 characterised by the pore distribution, e.g. inhomogeneous distribution of pores
• CPC Class Codes: C04B 38/06 by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
• CPC Class Codes: C04B 38/065 characterised by physical aspects, e.g. shape, size or porosity
• CPC Class Codes: C04B 38/069 Other materials, e.g. catalysts C04B33/13, C04B35/00 take precedence
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4564 Electrolytic or electrophoretic processes, e.g. electrochemical re-alkalisation of reinforced concrete desalination C04B41/53
• CPC Class Codes: C04B 41/5031 Alumina
• CPC Class Codes: C25D 13/02 with inorganic material
• CPC Class Codes: C25D 13/14 Tubes; Rings; Hollow bodies
• CPC Class Codes: H01M 8/1231 with both reactants being gaseous or vaporised
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides methods for producing hollow ceramic membranes by electrophoretic deposition. The hollow ceramic membranes may have a small cross-sectional area of about 1.0×10⁻⁵ mm² to about 25 mm². The cross-sectional configuration of the hollow ceramic membranes may be any geometry such as circular, square, rectangular, triangular or polygonal. The hollow ceramic membranes produced by the methods of the present invention may have multiple layers but always the innermost layer, or the first deposited layer is porous and made by electrophoretic deposition. Subsequent layers may be porous or non porous and deposited before or after sintering the first layer. If it is deposited after sintering, it may require additional sintering steps. Additional layers may be deposited by further electrophoretic deposition, sol-gel coating, dip coating, vacuum casting, brushing, spraying or other known techniques.

Claims

1. A method of producing a porous hollow ceramic membrane comprising the steps of;

(a) providing a suspension of a particulate ceramic material having an average particle size greater than about 150 nm in a non-aqueous liquid;

(b) electrophoretically depositing the particulate material onto an electrically conductive fibre core;

(c) drying the fibre core-bearing the deposited material; and

(d) sintering the fibre core bearing the deposited material at a temperature and for a length of time sufficient to combust the fibre core while producing a porous hollow ceramic membrane which has a density less than 95% of the density of the ceramic material.

2. The method of claim 1 wherein the fibre core is a bundle of individual fibres which is infiltrated by the particulate material upon electrophoretic deposition such that upon removal of the fibre core, the membrane comprises a hollow core comprising a plurality of elongate cylindrical pores.

3. The method of claim 1 wherein the fibre core is a fibre tow comprising a bundle of individual fibres and further comprising the step of coating the fibre core with an organic binder to prevent infiltration of the particulate material during electrophoretic deposition.

4. The method of claim 3 wherein the fibre core is coated with the organic binder by immersing the fibre core into a solution of the organic binder.

5. The method of claim 1 wherein the porosity of the membrane is controlled by controlling the duration and temperature of the sintering step.

6. The method of claim 1 wherein the porosity of the membrane is controlled by controlling the particle size, size distribution and/or the surface area of the ceramic material.

7. The method of claim 1 wherein the porosity of the membrane is controlled by adding sintering additives in the suspension where additives will deposit concurrently with the ceramic material.

8. The method of claim 1 wherein the porosity of the membrane is controlled by adding a combustible particulate material to the ceramic material which is concurrently deposited with the ceramic material, wherein said combustible material is removed by combustion during the sintering step.

9. The method of claim 8 wherein the combustible particulate material is chosen from the group consisting of carbon, carbon black and organic or polymeric compounds.

10. The method of claim 1 wherein the porosity of the membrane is controlled by controlling two or more of the factors chosen from the group consisting of:

(a) the duration and temperature of the sintering step;

(b) the particle size, size distribution and/or the surface area of the ceramic material;

(c) adding the sintering additives in the suspension where additives will deposit concurrently with the ceramic material; and

(d) adding a combustible particulate material to the ceramic material which is concurrently deposited with the ceramic material, wherein said combustible material is removed by combustion during the sintering step.

11. The method of claim 1 wherein the electrophoretic deposition step is repeated at least once using a ceramic particulate material that is different or has different characteristics such that a multi-layer ceramic hollow membrane where each layer has different characteristics results.

12. The method of claim 10 wherein the electrophoretic deposition step is repeated at least once using the same ceramic material but having a different particle size distribution and/or surface area such that a multi-layer ceramic hollow membrane having at least two layers having different porosities results.

13. The method of claim 10 wherein the electrophoretic deposition step is repeated at least once using the same ceramic material but with differing amounts of combustible particles in the suspension to provide a multi-layer ceramic hollow membrane having at least two layers having different porosities.

14. The method of claim 1 further comprising the step of immersing the fibre core into the particulate suspension once and withdrawing it in a vertical position before re-immersing the fibre core in the particulate suspension for the deposition step.

15. The method of claim 1 further comprising the step of immersing the fibre core into a liquid once and withdrawing it in a vertical position before immersing the fibre core in the particulate suspension for the deposition step.

16. The method of claim 1 wherein the non-aqueous liquid is selected from the group consisting of ethanol, methanol, isopropanol, butanol, acetone, butylamine, acetylacetone, methyl ethyl ketone and mixtures thereof.